Acetic Acid → HCID 19783238, compound

HRID 257556Notes

Reaction equation

HRID 257556 reaction equation
C([NH:5][S:6]([C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=1[C:15]1[CH:20]=[CH:19][C:18]([CH2:21][CH:22]([C:32](=O)[CH2:33][CH2:34][CH2:35][CH3:36])[C:23](=NOC)[C:24]([O:26][CH2:27][CH3:28])=[O:25])=[CH:17][CH:16]=1)(=[O:8])=[O:7])(C)(C)C.Cl.[Cl:39][C:40]1[CH:45]=[CH:44][C:43]([N+:46]([O-:48])=[O:47])=[CH:42][C:41]=1[NH:49][NH2:50].C(O)(=O)C>COCCO>[CH2:33]([C:32]1[C:22]([CH2:21][C:18]2[CH:19]=[CH:20][C:15]([C:10]3[CH:11]=[CH:12][CH:13]=[CH:14][C:9]=3[S:6](=[O:8])(=[O:7])[NH2:5])=[CH:16][CH:17]=2)=[C:23]([C:24]([O:26][CH2:27][CH3:28])=[O:25])[N:49]([C:41]2[CH:42]=[C:43]([N+:46]([O-:48])=[O:47])[CH:44]=[CH:45][C:40]=2[Cl:39])[N:50]=1)[CH2:34][CH2:35][CH3:36]

Participants

5

Reactant 3

HCID 176Acetic AcidHCID 53747773HCID 53747773, compoundHCID 67885116HCID 67885116, compound

Product 1

HCID 19783238HCID 19783238, compoundYield 49.5%

Reagents, catalysts & solvents 1

HCID 80192-MethoxyethanolSolvent

Conditions

Temperature
105 °C

Procedure

A mixture of 3.07 g (5.79 mmol) of ethyl 3-[[2'-(N-t-butylsulfamoyl)biphenyl-4-yl]methyl]-2-methoxyimino-4-oxooctanoate (from Step F), 5.00 g (22.3 mmol) of 2-chloro-5-nitrophenylhydrazine hydrochloride [prepared from 2-chloro-5-nitroaniline according to H. Stroh and G. Westphal, Chem. Ber., 96, 184 (1963)], 55 mL of glacial acetic acid, and 25 mL of 2-methoxyethanol was stirred under N2 at 105° C. for 20 hours. The cooled mixture was concentrated in vacuo and the residue was partitioned between 200 mL of 0.2N HCl and 200 mL of ethyl acetate. The organic layer was washed with H2O (200 mL), dried over Na2SO4, filtered, and concentrated. Flash chromatography of the residue twice on silica gel (first column eluted with 2% MeOH in CH2Cl2, second column eluted with 1% MeOH in CH2Cl2) to provide 1.71 g (47%) of the title compound as a viscous, orange oil; homogeneous by TLC in 98:2 CH2Cl2 --MeOH; mass spectrum (FAB) m/e 598 (M+1)+. 400 MHz 1H NMR (CDCl3) δ0.87 (t, J=7.3 Hz, 3H), 1.06 (t, J=7.1 Hz, 3H), 1.34 (m, 2H), 1.59 (m, 2H, partially obscured by H2O peak), 2.62 (t, J=7.8 Hz, 2H), 4.10 (s, 2H), overlapping 4.14 (q, J=7.0 Hz, 2H), 4.24 (s, 2H), 7.26 (d, J=8.2 Hz, 2H), 7.32 (dd, J=7.5, 1.3 Hz, 1H), 7.41 (d, J=8.2 Hz, 2H), 7.49 (m, 1H), 7.58 (m, 1H), 7.66 (d, J=8.8 Hz, 1 H), 8.14 (dd, J=7.9, 1.3 Hz, 1H), 8.26 (dd, J=8.8, 2.7 Hz, 1H), 8.36 (d, J=2.6 Hz, 1H).

Workup

  1. concentrationThe cooled mixture was concentrated in vacuo
  2. customthe residue was partitioned between 200 mL of 0.2N HCl and 200 mL of ethyl acetate
  3. washThe organic layer was washed with H2O (200 mL)
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-4b80509caa9e430fbeedf2214468b12e
Source dataset
uspto-grants-1993_11
Patent number
US05262412

Reaction notes

Loading…